DK172341B1 - Process for preparing hydrotreating catalyst from a hydrogel and catalyst prepared by the process - Google Patents

Abstract

Process for preparing highly active hydrotreating catalysts by incorporating a compound selected from the group consisting of nickel, cobalt and mixtures thereof, a heavy metal selected from the group consisting of molybdenum, tungsten and mixtures thereof, and a stabilizing amount of phosphorus into an alumina hydrogel. The final calcined catalysts have surface areas of at least 300 m<2>/g, at least 20% of the pore volume in pores having diameters greater than 35 nm and at least 20% of the pore volume in pores having diameters less than 7 nm.

Description

DK 172341 B1

The present invention relates to a process for producing highly active hydrotreating catalysts containing a catalytically effective amount of cobalt, nickel and mixtures thereof and a catalytically effective amount of a heavy metal selected from molybdenum, tungsten and mixtures thereof and a phosphorus compound, on an alumina compound. catalysts having surface areas of at least 300 m / g, at least 20% of the pore volume in pores with a diameter above 35 nm, and at least 20% of the pore volume in pores with a diameter below 7 nm. The invention further relates to catalysts prepared by such a method of said type.

In the catalytic treatment of petroleum raw materials, it is often desirable to change the pore structure 15 of the catalyst to accommodate different types of feed materials. For example, when treating feed materials without metals or with a low metal content, it may be technically and economically desirable to use catalysts with narrow pores. On the other hand, when treating high-metal feed materials, the metals have the ability to deposit on the catalyst surface and clog pores on conventional hydrotreating catalysts, resulting in a loss of catalytic activity for the removal of sulfur and nitrogen. In order to maintain the hydrotreating activity, it is necessary that the catalyst has a large surface area. To facilitate the diffusion of large components into and out of the catalysts and to counteract surface deposits of coke and metals, large pore diameters are required. These requirements necessitate the use of bimodal catalysts which have large surface areas and a considerable proportion of the pore volume in large pores. The large pores allow increased diffusion of large molecules into the catalyst, while the smaller pores that provide most of the surface area permit hydrotreating of the feedstock. Catalysts of this type can be used as hydrotreating catalysts, in particular DK 172341 B1 2 for residue / demetallization applications.

Surprisingly, it has been found that by a process of the above kind, one can produce hydrogel-derived catalysts with activities equal to or better than those of conventional techniques when compared on the basis of metal efficiency while having considerably lower densities than the conventionally produced catalysts. Two of the main advantages of the hydrogel pathway are 10 higher metal utilization and lower cost of producing catalysts compared to conventionally produced catalysts. The present hydrogel-derived catalysts have large surface areas, at least 300 m / g; at least 20% of the pore volume in pores with a diameter of 15 meters greater than 35 nm; and at least 20% of the pore volume in pores with a diameter less than 7 nm. Such catalysts are particularly suitable for residue / demetallization applications.

Accordingly, the process of the invention is characterized by (a) precipitating an aqueous solution of one or more aluminum salts by adjusting the pH of the solution to the range of 5.5-10 at a temperature between 20 and 90 ° C for at least 20 minutes, thereby forming a precipitate, (b) aging the precipitate at a temperature in the range 20-90 ° C for at least 0.1 hour at a pH in the range 8.0-12.0, (c) washing (d) mixing the precipitate with one or more compounds of an element selected from nickel, cobalt and mixtures thereof, of a heavy metal selected from molybdenum, tungsten and mixtures thereof and a phosphorus-containing compound in an amount of 0.2-35 1.5 moles of phosphorus per mole of heavy metal at a pH in the range of 4.0-10.0 and a temperature in the range of 25-100 ° C until the adsorption of the metal compounds to the DK 172341 B1 gel is sufficient to lead to a final catalyst containing 1-5 wt. % cobalt and / or nickel and 8-32% by weight heavy metal, (e) homogenizes the product of step (d), (5) extrudes the product of step (e), and (g) dries and calcines the product of step (f) at a temperature in the range of 300-900 ° C; Preferred embodiments of the present process are shown in subclaims 2-12; and the catalyst 10 of the invention is characterized in that it has been prepared by the process of the present invention.

In the process of the present invention, highly active hydrotreating catalysts are suitably prepared by incorporating one or more compounds of an element selected from nickel, cobalt and mixtures thereof, a heavy metal selected from molybdenum, tungsten and mixtures thereof, and a phosphorus-containing compound. an alumina-hydrogel-derived carrier prepared by titrating an aqueous solution of an acidic aluminum compound and an aqueous solution of a basic aluminum compound.

The alumina hydrogel can be prepared by titrating an aqueous solution of one or more aluminum salts with a suitable acidic or basic material or solution to induce precipitation of the alumina gel. It is known to those skilled in the art that the alumina gel can be prepared by titrating an acidic aluminum salt such as aluminum sulfate, aluminum nitrate or aluminum chloride in aqueous solution with a basic precipitation medium such as sodium hydroxide or ammonium hydroxide or by titrating an alkali metal aluminate such as aqueous solution of potassium aluminate or potassium aluminate with an acid precipitating medium such as hydrochloric or nitric acid. It will be obvious to those skilled in the art that setting the pH of the aluminum-containing solution to 5.5-10.0 causes precipitation of the aluminum residue as aluminum hydroxide or hydrated alumina.

According to a preferred embodiment, the alumina hydrogel is prepared by titrating an aqueous solution of DK172341 B1 4 an alkali metal aluminate and an aqueous solution of an acidic 5 aluminum salt, thereby precipitating an alumina gel. Suitable acidic aluminum salts are, for example, aluminum sulfate, aluminum nitrate and aluminum chloride. A preferred reagent is aluminum sulfate. Suitable alkali metal aluminates are sodium aluminate and potassium aluminate. The precipitation can be accomplished by adding an aqueous solution of the basic aluminum reagent to an aqueous solution of the acidic aluminum reagent, or the process can be reversed to add an aqueous solution of the acidic aluminum reagent to an aqueous solution of the basic aluminum reagent ( which is referred to as "sequential precipitation"). The precipitation by the process of the present invention is preferably carried out simultaneously by the addition of the acidic aluminum reagent and the basic aluminum reagent, thereby precipitating a hydrogel (referred to as "simultaneous precipitation").

The ranges and limitations set forth in the present disclosure and claims are those which are considered to be particularly marked by the present invention.

25 The temperature and pH of the precipitate are very variable in precipitation of the alumina materials in which the metals can be incorporated to form catalysts of desired physical qualities. Those of skill in the art will appreciate that changes in precipitation temperatures and pHs cause changes in the porosities. The optimal temperatures and pH values for the precipitation of the alumina materials can be determined with minimal routine experimental work. In the process of the present invention, the precipitation temperature is 20-90 ° C, preferably 50-85 ° C; in particular, 55-65 ° C, and the pH of the precipitate is in the range 5.5-10.0, preferably 5.5-8.0, especially 6.0-7.5.

The time required for the precipitation step appears to be critical for the formation of a catalyst with the desired bimodal pore size distribution. The required time period for the precipitation step is at least 20 minutes, preferably at least 30 minutes, especially at least 40 minutes. The upper limit of the time required for the precipitation step is not critical but is governed by financial considerations.

After precipitation, the pH of the slurry is adjusted to a pH in the range 8.0 to 12.0, preferably 9.0 to 11.0, in particular 9.5 to 10.5, and the resulting mass is aged at temperature in the range 20-90 ° C, preferably 50-85 ° C for at least 15 minutes. The upper limit of the aging time space is not critical and is usually determined based on economic considerations. Aging times are typically in the range of 0.1-10 hours, preferably 0.25-5 hours, especially 0.25-1 hours. Generally, alumina materials having acceptable properties are produced by keeping the aging temperature 20o substantially equal to the precipitation temperature.

After aging, the slurry is washed and routinely filtered to remove substantially anything that can be removed by water-soluble salts formed during the hydrogel precipitation. The preferred solvent for washing is water, although other solvents such as lower alkanols can be used.

After washing, the metal compounds are incorporated into the hydrogel. One method of adding the metal compounds to the hydrogel is resuspending, whereby the hydrogel is resuspended with a solution containing solubilized salts of a element selected from nickel, cobalt and mixtures thereof, and a heavy metal selected from molybdenum, tungsten and mixtures thereof and a phosphorus content. compound sufficient to deposit on the final catalyst 1-5 wt.% nickel and / or cobalt and 8-18 wt.% molybdenum or 10-32 wt.% tungsten. When mixtures of molybdenum and tungsten are used, the final catalyst typically contains 8-32% by weight of molybdenum and tungsten. However, the solution may contain amounts of nickel and / or cobalt and molybdenum or tungsten in excess of the amount required for deposition 5 of the aforementioned amounts of metal, which excess can be removed by washing or other technique after the resuspending step. A typical solution containing metal compounds can be prepared by combining a molybdenum and / or tungsten-containing solution with a nickel-10 and / or cobalt-containing solution. The metal-containing solution also contains a stabilizing amount of phosphorus. Typically, the metal-containing solution contains a phosphorus-containing compound in an amount of 0.2-1.5 moles of phosphorus per liter. moles of molybdenum or tungsten.

In this specification, the term "a phosphorus-containing compound" is generic and denotes both a phosphorus-containing compound and several phosphorus-containing compounds. Suitable phosphorous compounds are acids of phosphorus and their salts. Typical acids of phosphorus are phosphoric acid, phosphonic acid, phosphinic acid and phosphoric acid. The phosphorous compound is usually selected from phosphoric acid, a phosphate salt and mixtures thereof. Suitable phosphate salts are alkali metal phosphates, alkali metal hydrogen phosphates, ammonium phosphate and ammonium hydrogen phosph.

The molybdenum solution contains a water-soluble source of molybdenum oxide such as ammonium heptamolybdate or ammonium dimolybdate dissolved in water and optionally a phosphorus-containing compound. Hydrogen peroxide can also be used to help prepare solution in 30 certain cases. In a preferred method of preparing a molybdenum solution, hydro, gene peroxide is added to the solution in an amount in the range 0.1 to 1.0 mol of hydrogen peroxide per liter. mol molybdenum. Optionally, a suitable soluble amine compound such as monoethanolamine, propanolamine or ethylenediamine may be added to the molybdenum-containing solution to aid in stabilizing the solution.

DK 172341 B1 7

The tungsten-containing solution typically contains ammonium metal tungsten dissolved in water and optionally a phosphorus-containing compound. In a preferred process for preparing a tungsten-containing solution, hydrogen peroxide is added to the solution in an amount in the range of 0.1-1.0 moles of hydrogen peroxide per liter. mole of tungsten.

In addition, a suitable soluble amine compound such as monoethanolamine, propanolamine or ethylenediamine may be added to the tungsten-containing solution to help stabilize the solution.

The nickel-containing solution contains nickel salts dissolved in water and optionally a phosphorus-containing compound. Several different nickel compounds are suitable such as nickel nitrate, nickel acetate, nickel formate, nickel sulfate, nickel oxide, nickel phosphate, nickel carbonate, nickel chloride and nickel hydroxide. Two particularly suitable compounds are nickel nitrate and nickel carbonate.

The cobalt-containing solution contains cobalt salts dissolved in water and optionally a phosphorus-containing compound. Several different cobalt compounds are suitable such as cobalt nitrate, cobalt hydroxide, cobalt acetate, cobalt oxalate and cobalt oxide. The preferred cobalt compound is cobalt nitrate.

In another method of incorporating 25 metal compounds into the hydrogel, dry, water-soluble metal compounds of an element selected from nickel, cobalt and mixtures thereof are added, dry, water-soluble compounds of a heavy metal selected from molybdenum, tungsten and mixtures thereof, and a phosphorous compound. the hydrogel and mixes until dissolution and adsorption of the metal compounds and the phosphorus to the gel are substantially complete. The metal compounds of nickel and / or cobalt and molybdenum and / or tungsten are added to the hydrogel in amounts sufficient to incorporate in the finished catalyst 1-5 wt.% Nickel and / or cobalt and 8-18 wt.% Molybdenum or 10- 32 wt% tungsten. When mixtures of DK 172341 B1 8 molybdenum and tungsten are used, the finished catalyst contains 8-32% by weight molybdenum and tungsten.

Molybdenum is usually added to the hydrogel as a dry, water-soluble source of molybdenum such as ammonium heptamolybdate or ammonium dimolybdate. Tungsten is typically added to the hydrogel as ammonium meta tungstate. Nickel is preferably added to the hydrogel in the form of dry, water-soluble nickel nitrate, nickel acetate, nickel formate, nickel sulphate, nickel oxide, nickel phosphate, nickel carbonate, nickel chloride or nickel hydroxide, nickel nitrate and nickel carbonate. Cobalt is typically added to the hydrogel in the form of dry, water-soluble cobalt nitrate, cobalt hydroxide, cobalt acetate, cobalt oxalate or cobalt oxide, with cobalt nitrate being preferred. The phosphorus-containing compound is typically added, either wet or dry, to the hydrogel in an amount in the range of 0.2-1.5 moles of phosphorus per day. moles of molybdenum or tungsten. The phosphorus-containing compound is preferably added directly to the hydrogel as phosphoric acid, a phosphate salt or mixtures thereof. Suitable 20 phosphate salts are alkali metal phosphate, alkali metal hydrogen phosphate, ammonium phosphate and ammonium hydrogen phosphate. The phosphorus-containing compound and the dry nickel and / or cobalt salt can also be mixed prior to addition of the hydrogel.

In a preferred method of mixing the dry metal salts of nickel and / or cobalt and molybdenum and / or tungsten with the hydrogel, hydrogen peroxide is added to the mixture of dry metal salts and hydrogel in an amount of 0.1-1.0 moles of hydrogen peroxide. per. mol 30 molybdenum and / or tungsten. Optionally, a suitable amine compound such as monoethanolamine, propanolol or ethylenediamine may be added to the dry metal salt and hydrogel mixture to assist in stabilizing the metal salt and hydrogel mixture.

The dry metal salts of nickel and / or cobalt, molybdenum and / or tungsten and the phosphorus-containing compound (if added dry) are typically added to the hydrogel in the form of finite particles, usually of a size of 0.15. mm or less. Although particle size is not critical and larger particle sizes can be used, it is economically advantageous to use particles having a size of 0.15 mm or less.

It is also within the scope of the present invention to combine the two methods described above for the addition of metals to the hydrogel. For example, one metal may be added to the hydrogel as a dry salt and the other may be added in the form of a solution. Several perimts of this combination of the addition of dry Sclte and the addition of metal solutions are obvious to those skilled in the art.

Temperature and pH at the stage where the metal-containing solutions and / or the dry metal salts are mixed with the hydrogel are important variables in the preparation of hydrogel-derived catalysts having satisfactory densities and porosities. Normally, higher temperatures provide lower density catalysts. The mixing of the hydrogen with the metal-containing solutions or the dry metal salts is carried out at a pH in the range of 4.0-10.0, preferably 4.0-9.0, especially 4.0-8.0, and at a temperature of the range 25-100 ° C, preferably 25 25-80 ° C, until the incorporation of the metal compounds into the gel is sufficient to result in a final calcined catalyst containing 1-5% by weight nickel and / or cobalt and 8-32% by weight heavy metal selected from molybdenum, tungsten and mixtures thereof. Typically, mixing times for hydrogel and metal compounds will be in the range of 0.5-2 hours. Optionally, the resulting material can be washed to remove unadsorbed metals and routinely filtered.

After the addition of the metal compounds to the hydrogel, the resulting material is subjected to shear to produce a stiffened hydrogel composition. The displacement effect of the hydrogel particles is effected by passing the hydrogel through a homogenizer such as, for example, a spring-loaded homogenization valve.

The degree of shear stress can be determined numerically by passing the hydrogel through a spring loaded homogenization valve. A suitable degree of shear stress is usually produced at a pressure drop in the range of 34-550 bar, preferably 138-482 bar in a conventional spring loaded homogenizer such as a "Gaulin" 57 liters per liter. hour, 550 bar laboratory homogenizer. Shear action may also be effected by other means such as * e.g., using a high speed blender, but a hdmogenizer for continuous reprocessing is preferred. A suitable degree of shear stress is in all cases an effect which produces an extrudate of the hydrogel which does not deform substantially under its own weight when formed. Thus, the extrudate formed prior to drying and calcining will retain its shape and enable drying and calcining steps to be performed without any significant change in shape.

After shearing the hydrogel, the resulting material can be easily extruded through a nozzle having a diameter of 12.7-127 mm. It is usually preferred to extrude the outlet from the homogenizer directly through the nozzle using the counterpressure of the homogenizer as a driving force during extrusion.

When other means of shear influence are used, suitable pumping means may be used to extrude the material through the extrusion head.

After the extrusion, the extrudates are dried and calcined. Although it is possible to dry the extrudates in a single step, it is preferred that the extrudates be dried in several steps. In multi-stage drying, a first drying step, so-called "skin drying", is performed to remove a substantial amount of the water and form a dried skin on the surface of the extrudate.

Skin drying is carried out (suitably at a temperature in the range of 100-300 ° C, preferably 120-200 ° C. Such skin drying extrudates can be handled and / or stored if desired without serious degradation of their structure prior to final processing. The final drying is carried out in a conventional manner, it can be carried out by forced stretch drying, vacuum drying, air drying or the like. Drying temperatures are not critical and depend on the particular means used in the drying. Drying temperatures are usually in the range of 50 -200 ° C.

After drying, the material is calcined to give the final catalyst. The material can be calcined in an oxidizing or neutral atmosphere, although an air atmosphere is preferred. However, if binders and / or lubricants are used, the material is heated in an oxygen-containing atmosphere, preferably air, to burn out the binders and lubricants. The calcination temperatures are 300-900 ° C. Drying, calcining and burnout can be combined in one or two steps. Often, the calcination and / or burn-out stages 20 are combined using an oxygen-containing atmosphere.

The finished catalysts were found to have surface area greater than 300 m / g, nitrogen pore volume of 0.4-1.2 ml / g and with at least 20% of their mercury pore volume in pores larger than 35 nm and at least About 20%, preferably 35%, of their mercury pore volume in pores less than 7 nm in diameter. The metal content of the finished catalysts is in the range of 1-5 wt% nickel and / or cobalt, preferably 2.5-4 wt% nickel and / or cobalt and 8-18 wt%, preferably 10-14 wt% 30 molybdenum or 10- 32 wt%, preferably 18-26 wt% tungsten.

The catalysts prepared in accordance with the present invention may suitably be used for hydrocarbon conversion processes such as hydrocracking, hydro-treatment, isomerization, hydrogenation, dehydrogenation, oligomerization, alkylation, dealkylation and the like.

DK 172341 B1 12

The catalysts prepared in accordance with the present invention are generally used for the hydrotreating and / or hydrocracking of crude materials containing volatile material from petroleum ether for 5 petroleum residues, incl. materials derived from tar sands, shale oil and the like. Reaction temperatures are typically in the range of 150-480 ° C, preferably 260-455 ° C. Reaction pressures are usually in the range of 14-240 bar, preferably 40-174 bar. The reactions are usually carried out at room rates in the range of 0.05 to 15 reciprocal hours.

There are many uses for these raw materials after treatment with the catalysts prepared in accordance with the present invention. Depending on the particular feed material treated, suitable applications are conversion unit feed materials such as thermal cracking and hydrocracking, or finished products such as gasoline, diesel fuel, airplane turbine fuel, furnace oil, solvents, fuel oils and asphalt.

The process for preparing catalysts in accordance with the present invention is elucidated by the following examples, the comparative examples illustrating catalyst preparation by the prior art.

25

Example 1 99.0 kg of aluminum sulfate solution was prepared by solubilizing 11.3 kg of gibsite (α-alumina trihydrate, 34% LOI) in 87.7 kg of 27% sulfuric acid at a temperature slightly above 100 ° C. The solution was allowed to cool to 60 ° C prior to use. 76.4 kg of sodium aluminate solution was prepared by solubilizing 28.2 kg of gibsite (α-alumina trihydrate, 34% LOI) in 48.2 kg of 36% sodium hydroxide at a temperature slightly above 115 ° C.

This solution was allowed to cool to 60 ° C prior to use. These two solutions were measured under computer control in a precipitation vessel containing 140 kg of deionized water maintained at 60 ° C, maintaining a constant pH of 7.0 and a temperature of 60 ° C. The duration of precipitation was set at 45 minutes. After the precipitation step was completed, excess sodium aluminate solution (13.5 kg) was added to the slurry to raise the pH to the desired aging pH of 10.3. A total of 66.7 kg of acid and 54.9 kg of base were used. The slurry was aged for 1 hour at elevated pH. The slurry was then filtered in a single step on a horizontal belt vacuum filter (0.3 x 3 m) and washed with deionized water. The resulting alumina hydrogel usually had a water content of 75-90% based on the dry weight of alumina.

To a container equipped with a high-speed stirrer was added a portion of alumina hydrogel prepared in 45 minutes of precipitation (2500 g, 84.0% LOI, based on 400 g dry weight), 360 g water, 99 , 92 g of cobalt nitrate hexahydrate, 85% phosphoric acid (100.73 20 g), 161.78 g of ammonium heptamolybdate, 48 ml of 30% hydrogen peroxide and 27.1 g of monoethanolamine. The pH was adjusted to 6.5 by NH 2 OH. The mixture was stirred vigorously to "liquefy" the hydrogel. After 2 hours of reaction at 25 ° C, the catalyst hydrogel slurry was passed through a "Gaulin" model 15M Lab homogenizer with a pressure drop of 413 bar. The solidified material from this homogenization step was extruded using a small hand extruder. Drying of the extrudate at 120 ° C was followed by calcination 30 at 510 ° C for 2 hours. The properties of the catalyst are shown in Tables I and II.

Example 2 35 99.0 kg of aluminum sulfate solution was prepared by solubilizing 11.3 kg of gibsite (α-alumina trihydrate, 34% LOI) in 87.7 kg of 27% sulfuric acid at a temperature slightly above 100 ° C. The solution was allowed to cool to 60 ° C before use. 76.4 kg of sodium aluminate solution was prepared by solubilizing 28.2 kg of gibsite (α-alumina trihydrate, 34% LOI) in 48.2 kg of 36% sodium hydroxide at a temperature slightly above 115 ° C. This solution was also allowed to cool to 60 ° C before use. These two solutions were measured under computer control in a precipitation vessel containing 140 kg of deionized water maintained at 60 ° C, maintaining a constant pH of 7.0 and a temperature of 60 ° C. The duration of precipitation was set at 45 minutes. After the precipitation step was completed, excess sodium aluminate solution (7.1 kg) was added to the slurry to raise the pH to the desired aging pH of 9.9.

A total of 71.0 kg of acid and 50.9 kg of base were used. The slurry was aged for 1 hour at elevated pH. The slurry was then filtered in a single step on a horizontal belt vacuum filter (0.3 x 3 m) and washed with deionized water. The resulting alumina hydrogel usually had a water content of 75-90% on the basis of the alumina dry weight.

To a container equipped with a high-speed stirrer was added a portion of alumina hydrogel prepared over 45 minutes of precipitation (4000 g, 25.77% LOI, based on a dry weight of 769 g), 100 g water, 133.76 g nickel nitrate hexahydrate, 120.57 g 85% phosphoric acid, 238.49 g ammonium heptamolybdate, 76 ml 30% hydrogen peroxide and 43.23 g monoethanolamine. The pH of the mixture was 5.9. The mixture was stirred vigorously to "melt" the hydrogel. After 2 hours of reaction at 25 ° C, the catalyst hydro slurry was passed through a "Mantin Gaulin" model 15M Lab homogenizer using a pressure drop of 413 bar. The solidified material from the homogenizer was extruded using a small manifold and nozzle system produced for the purpose for the homogenizer. Drying of the extrudate at 120 ° C was followed by calcination at 510 ° C for 2 hours. The properties of the catalyst are shown in Tables I and II.

Comparative Example A

99.0 kg of aluminum sulfate solution was prepared by solubilizing 11.3 kg of gibsite (α-alumina trihydrate, 34% LOI) in 87.7 kg of 27% sulfuric acid at a temperature slightly above 100 ° C. The solution was allowed to cool 10 to 60 ° C before use. 76.4 kg of sodium aluminate solution was prepared by solubilizing 28.2 kg of gibsite (α-alumina trihydrate, 34% LOI) in 48.2 kg of 36% sodium hydroxide at a temperature slightly above 115 ° C. This solution was also allowed to cool to 60 ° C before use. These two solutions were measured under computer control in a precipitation vessel containing 121 kg of deionized water maintained at 60 ° C, maintaining a constant pH of 7.0 and a temperature of 60 ° C. The duration of precipitation was set at 15 minutes. After completion of the precipitate, excess sodium aluminate solution (13.5 kg) was added to the slurry to raise the pH to the desired aging pH of 10.3. The total dissolution amounts used were 45.0 kg of acid and 33.7 kg of base. The slurry was aged for 1 hour at elevated 25 pH. The slurry was then filtered in a single step on a horizontal belt vacuum filter (0.3 x 3 m) and washed with deionized water. The resulting alumina hydrogel generally had a water content of 75-90% based on the dry weight of alumina.

To a container equipped with a high speed stirrer was added a portion of the alumina hydrogel prepared during 15 minutes of precipitation (4000 g, 84.98% LOI, based on a dry weight of 600 g), 103.12 g of cobalt nitrate hexahydrate , 93.05 g of 85% sulfuric acid, 176.67 g of ammonium heptamolybdate, 59 ml of 30% hydrogen peroxide and

33.4 g of monoethanolamine. The pH was adjusted to pH

7.3 with NH 3 OH. The mixture was stirred vigorously to "melt" the hydrogel. After 2 hours of reaction at 25 ° C, the catalyst hydro slurry was passed through a "Gaulin" model 15M Lab homogenizer at a pressure drop of 413 bar. 5 was then extruded using a small manifold and nozzle system for the homogenizer, drying the extrudate at 120 ° C followed by calcination at 510 ° C for 2 hours The properties of the catalyst are shown in Tables I and II.

10

Comparative Example B

99.0 kg of aluminum sulfate solution was prepared by solubilizing 11.3 kg of gibsite (α-alumina trihydrate, 34% LOI) in 87.7 kg of 27% sulfuric acid at a temperature slightly above 100 ° C. The solution was allowed to cool to 60 ° C before use. 76.4 kg of sodium aluminate solution was prepared by solubilizing 28.2 kg of gibsite (ot-alumina trihydrate, 34% LOI) in 48.2 kg of 36% sodium hydroxide at a temperature slightly above 115 ° C. This solution was also allowed to cool to 60 ° C before use. The two solutions were measured under computer control in a precipitation vessel containing 121 kg of deionized water maintained at 60 ° C, maintaining a constant pH of 7.0 and a temperature of 60 ° C. The duration of precipitation was fixed at 15 minutes. After completion of the precipitation, excess sodium aluminate solution (8.2 kg) was added to the slurry to raise the pH to the desired aging pH of 10.0. The total dissolution amounts used were 47.5 kg of acid and 33.7 kg of base. The slurry was aged for 1 hour at elevated pH. The slurry was then filtered in a single step on a horizontal belt vacuum filter (0.3 x 3 m) and washed with deionized water. The resulting alumina hydrogel usually had a water content of 75-90% based on the alumina dry weight.

DK 172341 B1 17

To a container equipped with a high-speed stirrer was added a portion of alumina hydrogel prepared over 15 minutes of precipitation (4000 g, 85.34% LOI, based on a dry weight of 586 g), 126.27 g of nickel nitrate hexahydrate. , 94.60 g of 85% phosphoric acid, 203.10 g of ammonium heptamolybdate and 33.98 g of monoethanolamine. The pH was adjusted to 6.3 with NH 2 OH. The mixture is stirred vigorously to "melt" the hydrogel. After 1.5 hours of reaction at 25 ° C, the catalyst hydrogel slurry was passed through a "Gaulin" model 15M Lab homogenizer at a pressure drop of 413 bar. The solidified material from the homogenization was then extruded using a small manifold and nozzle system made for the purpose for the homogenizer. Drying of the extrudate at 120 ° C was followed by calcination at 510 ° C for 2 hours.

The properties of the catalyst are shown in Tables I and II.

A comparison of the above catalyst preparations shows that the catalyst preparation techniques described in Examples 1 and 2 are very similar to the techniques described in Comparative Examples A and B except that the duration of the precipitation steps of Examples 1 and 2 was 45 minutes while the duration of the the precipitation steps of Comparative Examples A and B were 15 minutes. As previously mentioned, the duration of the precipitation step is critical for the formation of a catalyst with at least 20% of its pore volume in pores with a diameter greater than 35 nm and at least 20% of its pore volume in pores with a diameter less than 7 nm. This is evidenced by the pore size distributions given in Table II. As seen from Table II, the catalysts prepared as set forth in Examples 1 and 2 have at least 20% of their pore volume in pores with a diameter greater than 35 nm and at least 20% of their pore volume in pores with a diameter less than 7 nm, i. a bimodal pore size distribution, while the catalysts prepared as described in Comparative Examples A and B have 80% of their pore volume in pores with dia 18 meters less than 7 nm, ie. a unimodal pore size distribution.

Comparative Example C

A catalyst was prepared using a non-hydrogel technique. The properties of the commercially available catalyst are shown in Tables I and II.

10 Catalyst Testing

Catalyst samples were used to hydro-treat a catalytically-cracked heavy gas oil (CCHGO) in a reactor with the worst escape. 10 ml of the appropriately extruded catalyst was crushed and sieved to 0.3-1 mm (16-45 mesh), diluted with silicon carbide and placed in a typical seepage flow reactor. The catalyst was pre-sulphated with a 5% S 2 S / H 2 O (v / v) gas mixture at 371 ° C for 2 hours before testing. A CCHGO was passed over the catalyst at 357 ° C and a partial hydrogen pressure of 58.6 bar with a H 2 / oil ratio equal to 4.0. Measured rate constants include hydrogenation, denitrification and desulfurization and are given relative to the non-hydrogel catalyst 25 (Comparative Example C) and are calculated on the basis of the total metal content of the catalyst. The specific catalyst performance characteristics are shown in Table III.

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in DK 172341 B1 21 a) The time at which the acidic and basic reagents were mixed.

b) Measured using an "Orion" ® 231 pH meter and "Orion" ® electrodes.

5 c) A volume of 209 ml fully precipitated in a measuring beaker and weighed.

d) Measured using an "Orion" ® 231 pH meter and "Or ion, MV electrodes.

e) BET (S. Brunauer, P.Y. Emmet and E. Teller, J.Am.

10 Chem.Soc., 6_0, 309-316 (1938)) by nitrogen adsorption / desorption, "Micromeritics" Digisorb 2500 instrument.

i f) With nitrogen adsorption, "Micromeritics" Digisorb 2500 instrument.

G) Weight% determined by neutron activation analysis or atomic absorption spectroscopy.

h) Weight% determined by neutron activation analysis or atomic absorption spectroscopy.

i) Weight% determined by neutron activation assay or atomic absorption spectroscopy.

j) Determined by mercury penetration to 4136 bar using a "Micromeritics" Autopore 9210 and using a contact angle of 130 ° and 0.473 N / m surface tension of mercury, the figures quoted are percent pore volume.

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Claims (13)

A process for producing highly active hydrotreating catalysts containing a catalytically effective amount of cobalt, nickel and mixtures thereof, and a catalytically effective amount of a heavy metal selected from molybdenum, tungsten and mixtures thereof, and a phosphorus compound, on an alumina carrier having surface catalysts. at least 300 m / g, at least 20% of the pore volume in pores with a diameter above 10 35 nm and at least 20% of the pore volume in pores with a diameter below 7 nm, characterized in that (a) an aqueous solution of one or more aluminum salts is precipitated by adjusting the pH of the solution to the range of 5.5-10 at a temperature between 20 and 90 ° C for at least 20 minutes, thereby forming a precipitate, (b) aging the precipitate at a temperature in the range 20- (C) washes the precipitate with one or more compounds of an element selected from nickel, cobalt and g of mixtures thereof, of a heavy metal selected from molybdenum, tungsten and mixtures thereof, and a phosphorus-containing compound in an amount of 0.2 to 1.5 moles of phosphorus per gram. mole of heavy metal at a pH in the range of 4.0-10.0 and a temperature in the range of 25-100 ° C until the adsorption of the metal compounds to the gel is sufficient to lead to a final catalyst containing 1-5% by weight of cobalt and / or nickel and 8-32% by weight of heavy metal, (e) homogenizes the product of step (d), (f) extrudes the product of step (e), and (g) dries and calcines the product of step (f) at 35 a temperature in the range of 300-900 ° C. DK 172341 B1 Process according to claim 1, characterized in that in step (a), an aqueous solution of an acidic aluminum salt is titrated with an aqueous solution of a basic aluminum compound at a pH in the range between 5.5 and 10.0 to a temperature in the range of 20-90 ° C for at least 20 minutes, thereby forming a precipitate, and in step (d) mixing the precipitate with one or more solutions containing solubilized salts of a heavy metal selected from molybdenum, 10 tungsten and mixtures thereof. a element selected from nickel, cobalt and mixtures thereof, and a phosphorus-containing compound in an amount of 0.2-1.5 moles of phosphorus per mole of heavy metal at a pH in the range of 4.0 to 9.0 and a temperature in the range of 25-100 ° C until adsorption of the metal salts to the gel is sufficient to result in a final catalyst containing 1-5 wt. % nickel and / or cobalt and 8-32% by weight heavy metal. Process according to claim 2, characterized in that in step (d), instead of with the said solutions, the precipitate is mixed with dry, water-soluble salts of a element selected from nickel, cobalt and mixtures thereof, a heavy metal selected from molybdenum , tungsten and mixtures thereof, and a phosphorus-containing compound in an amount of 0.2-1.5 moles of phosphorus per mole of heavy metal at a pH in the range of 4.0-9.0 and a temperature in the range of 25-100 ° C to give a finished catalyst containing 1-5% by weight nickel and / or cobalt and 8-32% by weight heavy metal. Process according to claim 2, characterized in that, in step (d), instead of said solutions, a dry, water-soluble salt of a heavy metal selected from molybdenum, tungsten and mixtures thereof is mixed with a mixture of a dry, water-soluble salt selected from nickel, cobalt and mixtures thereof, and a phosphorus-containing compound in an amount of 0.2-1.5 moles of phosphorus per phosphorus. moles of heavy metal with the precipitate at a pH in the range of 4.0-9.0 and a temperature in the range of 25-100 ° C to form a final catalyst containing 1-5% by weight of nickel and / or cobalt and 8-32% by weight % heavy metal. Process according to claim 1, characterized in that in step (a), an aqueous solution of an acidic aluminum salt selected from aluminum sulfate, aluminum nitrate and aluminum chloride is titrated with an aqueous solution of a basic aluminum compound 10 selected from sodium aluminate and potassium aluminate at a pH. -value in the range 5.5-8.0 and a temperature in the range 20-90 ° C for at least 30 minutes to form a precipitate, and in step (d) mix the precipitate with one or more solutions containing solubilized molybdate-15 or dimolybdate salts and nickel or cobalt salts as well as phosphoric acid in an amount of 0.2-1.5 mole phosphorus per mole of molybdenum at a pH in the range of 4.0-8.0 and a temperature in the range of 25-100 ° C until the adsorption of the metal salts to the gel is sufficient to give a final catalyst containing 2.5-4% by weight nickel or cobalt and 10-14 wt.% molybdenum. Process according to claim 5, characterized in that in step (d), instead of said solutions, a dry, water-soluble molybdate or dimolybdate salt is mixed, a mixture of a dry, water-soluble nickel or cobalt salt and phosphoric acid in a amount of 0.2-1.5 moles of phosphorus per mole of molybdenum with the precipitate at a pH in the range of 4.0-8.0 and a temperature in the range of 25-100 ° C to form a final catalyst containing 2 , 5-4 wt% nickel or cobalt and 10-14 wt% molybdenum. Process according to claim 1, characterized in that in step (d), the precipitate is mixed with dry, water-soluble salts of a element selected from nickel, cobalt and mixtures thereof, a heavy metal DK 172341 B1 selected from molybdenum, tungsten and mixtures thereof. and a phosphorus-containing compound in an amount of 0.2-1.5 moles of phosphorus per mole of heavy metal at a pH in the range of 4.0 to 9.0 and a temperature in the range of 25-100 ° C to form a final catalyst containing 1-5% by weight nickel and / or cobalt and 8-32% by weight heavy metal. Process according to claim 1, characterized in that in step (d) a dry, water-soluble salt of a heavy metal selected from molybdenum, tungsten and mixtures thereof is mixed, a mixture of a dry, water-soluble salt selected from nickel. , cobalt and mixtures thereof and a phosphorus-containing compound in an amount of 0.2-1.5 moles of phosphorus per liter. moles of heavy metal with the precipitate at a pH in the range 4.0-9.0 and a temperature in the range 25-100 ° C to form a final catalyst containing 1-5% by weight of nickel and / or cobalt and 8-32 weight% heavy metal. Process according to claim 1, characterized in that in step (a), an aqueous solution of an acidic aluminum salt selected from aluminum sulfate, aluminum nitrate and aluminum chloride is precipitated with an aqueous solution of a base at a pH in the range. 5.5 to 8.0 and a temperature in the range of 20-90 ° C for at least 30 minutes to form a precipitate, and in step (d) mix the precipitate with one or more solutions containing solubilized molybdate or dimolybdate salts and nickel or cobalt salts and phosphoric acid in an amount of 0.2-1.5 moles of phosphorus per liter. moles of molybdenum at a pH in the range of 4.0 to 8.0 and a temperature in the range of 25 to 100 ° C until the adsorption of the metal salts to the gel is sufficient to result in a final catalyst containing from 2.5 to 4% by weight nickel or cobalt and 10-14 wt.% molybdenum. Process according to claim 9, characterized in that in step (d), instead of said DK 172341 B1 solutions, a dry, water-soluble molybdate or dimolybdate salt is mixed, a mixture of a dry, water-soluble nickel or cobalt salt. and phosphoric acid in an amount of 0.2-1.5 moles of phosphorus per liter. moles of molybdenum having the precipitate at a pH in the range 4.9-8.0 and a temperature in the range 25-100 ° C to form a final catalyst containing 2.5-4% by weight nickel or cobalt and 10-14 wt% molybdenum. Process according to claim 1, characterized in that in step (a), an aqueous solution of an acid is titrated with an aqueous solution of a basic aluminum compound selected from sodium aluminate and potassium aluminate at a pH in the range. 5.5 to 8.0 at a temperature in the range of 20-90 ° C for at least 30 minutes to form a precipitate and in step (d) mix the precipitate with one or more solutions containing solubilized molybdate or dimolybdate salts and nickel or cobalt salts and phosphoric acid in an amount of 0.2-1.5 mol of phosphorus per moles of molybdenum at a pH in the range of 4.0-8.0 and a temperature in the range of 25-100 ° C until the adsorption of the metal salts to the gel is sufficient to lead to a final catalyst containing 2.5-4% by weight nickel or cobalt and 10-14 wt.% molybdenum. Process according to claim 1, characterized in that in step (a), precipitate is formed in an aqueous solution of an acid with an aqueous solution of a basic aluminum compound selected from sodium luminate and potassium aluminate at a pH in the range. 5.5 to 8.0 at a temperature in the range of 20-90 ° C for at least 30 minutes to form a precipitate and in step (d) mix a dry, water-soluble molybdate or dimolybdate salt and a mixture of a dry , water-soluble nickel or cobalt salt and phosphoric acid in an amount of 0.2-1.5 moles of phosphorus per mole molybdenum with the precipitate at DK 172341 B1 a pH in the range 4.0-8.0 and a temperature in the range 25-100 ° C to form a finished catalyst containing 2.5-4% by weight nickel or cobalt and 10 -14% by weight molybdenum. A catalyst containing a catalytically effective amount of cobalt, nickel and mixtures thereof, and a catalytically effective amount of a heavy metal selected from molybdenum, tungsten and mixtures thereof, and a phosphorus compound, on an alumina support, said catalyst having a surface area of at least 300 m / g, at least 20% of the pore volume in pores with a diameter over 35 nm and at least 20% of the pore volume in pores with a diameter below 7 nm, characterized in that the catalyst has been prepared by a process according to one or more of the claims 1-12.